Water-insoluble monoazodyestuffs



UNITED STATES PATENT OFFICE 2,644,814 WATER-INSOLUBLE MONOAZODYESTUFFS Ernst Fischer, Offenbach am Main, Germany, as-

signor to Farbwerke Hoechst A. G. vormals Meister Lucius und Briining, Frankfurt, Germany No Drawing. Application January 9, 1951, Serial No. 205,218. In Germany January 20, 1950 I 6 Claims. (01. 260-193) This invention relates to new water-insoluble monaozo-dyestuffs and more particularly to compounds of the following general formula 2 and halogen, with an acetoacetic acid arylide of the general formula wherein X stands for a substituent of the group fi X consisting of lower alkyl and lower alkoxy, and N Y stands for a substituent of'the group consist- 1 ing of lower alkoxy and halogen; and Z stands CHFCO OH OO'NH I for a substituent of the group consisting of lower alkyl, lower allcoxy and halogen, at least one wherein each V stands for a substituent of the group consisting of hydrogen, lower alkyl, lower alkoxy and halogen, and X stands for a substituent of the group consisting of lower alkyl and lower alkoxy, and Y stands for a substituent of the group consisting of lower alkoxy and halogen, and 2 stands for a substituent of the group consisting of lower alkyl, lower alkoxy and halogen, at least one of the substituents X, Y and Z standing for lower alkoxy and one of the substituents Y and Z standing for halogen, being water-insoluble yellow powders and producing yellow tints having good properties of fastness, being especially suitable for coloring plastic masses composed of organic compounds of high molecular Weight, for producing colored lacquers fast to oil and light and for producing spun-dyed artificial silk.

According to this invention pigment dyestuffs are made by coupling a diazo compound of an amine of the general formula OCHa V in which V stands for a substituent of the group consisting of hydrogen, lower alkyl, lower alkoxy of the substituents X, Y and Z standing for lower allzoxy and-one of the substituents Y and Z standing for halogen. Preferably the amine from which the diazo component is made has the general formula SIO zNH. Oe 5 O C Ha CHaO Q NH,

The new dyestuffs produce yellow tints having good properties of fastness. They are especially suitable for coloring plastic masses composed of organic compounds of high molecular weight, for example, urea-formaldehyde, phenol-formaldehyde. or amine-formaldehyde condensation products, polyvinyl compounds, rubber and the like, and they can also be used for producing coloring lacquers fast to oil and light, and can be used with advantage, by adding them to spinning solutions, for producing spun-dyed artificial silk of cellulose acetate or of viscose.

The dyestufis of the present invention are distinctly superior with regard to their tendency to bleed into undyed polymerization products from vinyl chloride, to the known dyestuffs described in German specifications Nos. 637,019 and 637,089 for the manufacture of which the same azo components are used.

The following examples illustrate the invention, the parts being by weight unless otherwise stated:

Example 1 15.4 parts of 1-amino-2:5-dimethoxybenzene- 4-sulphonic acid phenyl amide are diazotized in the usual manner. In order to eliminate the excess of mineral acid the diazo solution is mixed with sodium acetate, and it is then stirred into an aqueous suspension of 13.6 parts of l-acetoacetyl-amino-2:5 dimethoxy 4 chlorobenzene, which has been obtained by dissolving the latter compound in dilute caustic soda solution and precipitating it with acetic acid. When the coupling has ceased, the resulting dyestuff is separated by filtration, washed well and dried. It is a yellow powder and has the structural formula SOzNILCdHl O CH:

CHzO

[I O OH: CHr-C O-'CHCO.NH

QCH';

The resulting dyestuff may be used for coloring a polymerization product of vinyl chloride in the following manner:

100 parts of a polymerization product of vinyl chloride, 50 parts of phthalic acid n-dibutyl es- Example 2 15.4 parts of 1-amino-2:S-dimethoxybenzene- 4-sulph0nic acid phenyl amide are diazotized in the usual manner. The diazo solution is rendered neutral to Congo with sodium acetate, and then stirred into a suspension of 12.8 parts of 1 acetoacetylamino 2 methoxy 4 chloro- S-methylbenzene, prepared by dissolution of the latter compound in caustic soda solution and precipitation with acetic acid. The resulting yellow dyestuff is separated by filtration, washed well and dried. It possesses the structural formula It can be used for coloring rubber in the following manner: 2 per cent of the resulting azo dyestuff are worked on rollers into a mixture of rubber, filling material, sulphur and a vulcanization accelerator. The mass is vulcanized in a hot press, and then has a yellow color, which has a good fastness to light and neither eflioresces nor bleeds when in contact with white rubber.

By immersing a mixture of rubber, the usual additions and 0.5 per cent. of the azo dyestuff in a. solution of sulphur monochloride in benzene and vulcanizing in the cold, there is obtained a mass of which the coloring has similar properties.

Example 3 A yellow dyestuff is prepared in the manner described in the preceding examples from the diazo compound of 16.1 parts of 1-amino-2z5- dimethoxybenzene-4-sulphonic acid (2 me thyl) -phenyl amide and 12.8 parts of l-acetoacetylamino-Z-methoxyi-chloro 5 methylbenzene. Lacquers prepared with the resulting dyestuif produce yellow tints of good fastness to light and oil.

Alternatively, the coupling may be carried out in the presence of a vehicle suitable for the manufacture of colored lacquers. white and 1 part of the azo dyestuff are mixed together.

The mixture is hardened by treatment with formaldehyde, whereby a horn-like mass is obtained, which has a yellow coloration of good fastness to light.

Example 4 The dyestufi? from 15.5 parts of 1-amino-2z5- dimethoxybenzene-4-sulphonic acid phenyl amide and 16.8 parts of l-acetoacetylamino-Z:5-diethoxy-l-chlorobenzene prepared in the manner described in Example 1, which is a yellow In order to produce colored casein artificial horn the above pigment dyestuff may be used as follows:

200 parts of rennet casein, 8 parts of zinc powder, is used for coloring in the manner illustrated in that example a polymerization product of vinyl chloride. The yellow color of the resulting product is fast to light, and does not bleed out into the undyed polymerization product Example 5 By using in Example 1, instead or 13.6 parts of l-acetoacetylamino-z:5-dimethoxy-4-chlorobenzene, 15.8 parts of 1-acetoacetylamino2:5 dimethoxyi-bromobenzene there is obtained a dyestuff having a similar tint. 0.5 part of this dyestufi is added to parts of a condensation product of urea and formaldehyde, which contains 30 per cent. of wood meal as a filling material, and the whole is ground in a ball mill for 12 hours. The mass is then placed in a press and pressing and hardening to form the desired moulded structure are carried out in 5 minutes at C. under pressure.

In the following table are mentioned further components which can be-used in the present process and the tints of the monoazo dyestuffs so obtainable. All these dyestuffs likewise possess good properties of fastness.

Diem-component Azo-component Tint 1 Amino 2:5 dimethoxy benzene 4 sul- 1 Acetoacetylamino 2:5 diethoxy 4 Yellow.

phonic acid phenylamide. bromo-benzene.

Do 1 acetoacetylamlno -2- methyl -4 -chloro- Do.

5-methoxybenzene. 1 amino 2:5 dimethoxy benzene 4 sul- 1 acetoacetylamino 2:5 dimethoxy- 4 Do.

phonic acid-(2-methyl)-pheny1amide. chlorobenzene. 1 amino 2:5 dimethox) benzene 4 sul- .do Do.

phonic acid-(2:4-dimethyl)-phenylamide. 1 amino 2:5 dimethoxy benzene 4- sul- 1 acetoaeetylamino 2:4 dlmethoxy 5 Do.

phonic acid-phenylamide. chlorobenzene.

Do 1 acetoacetylammo-2-methoxy-4-bromo- Do,

fi-methylbenzene. 1 amino -2:5 dlmethoxy benzene 4 -sul- 1 acetoacetylamino 2:5 dlmethoxy -4 Do.

phonic acid-(3-ohloro-)-phenylamide. chlorobenzene.

Do 1 acetoacetylammo-2-methoxy-4-chlorc- Do,

5-methylbenzene. 1 amino 2:5 dimethox benzene 4 -suldo Do,

phonic acid-(4'-bromo -pheny1amide. 1 amino 2:5 dimethoxy benzene 4 -sull acetoacetylemlno 2:6 dimethoxy 4 Do.

phonic aoid-(4-chl0ro)-pheny]amide. chlorobenzene. 1 amino 2:5 dimethoxy benzene 4 sul- .-.do Do,

phonic acid (2z5 dimethoxy 4 ch1oro)- phenylamide. 1 amino 2:5 dimethoxy benzene 4 sul- .d0 Do.

phoriic acid-(2-methyl-4-eh1oro)-pl1enylam e.

The second dyestuff listed in the foregoing table has the structural formula 0011 and the fifth dyestuff listed has the structural formula wherein each V stands for a substituent of the group consisting of hydrogen, lower alkyl, lower alkoxy and halogen, and X stands for a substituent of the group consisting of lower alkyl and lower alkoxy, and Y stands for a substituent of the group consisting of lower alko'xy'and halogen, and Z stands for a substituent of the group consisting of lower alkyl, lower alkoxy' and haloen, at least one of the substituents X, Y and Z standing for lower alkoxy and one ofthe substituents Y and Z standing for halogen, said dyestuffs being water insoluble yellow powders.

2. The monoazo-dyestufl's of the following general formula so NlELC H I 6 5 OCH' SOzNHJJuH C'HaO OOH.

60 N OOH; CHlO I CHr-COCHCO.NH n x on N O CErCO--( JH-CONH- 1 I claim: Y 1. The monoazodyestufis of the following general formula SOzNH V 0CH3 -v omo- V N ll 7 3. The monoazo dyestufl of the following 5. The monoazo dyestuf! of the following formula: formula:

SO$.NH.CH:

SO|NH.CQH;

CH|O r OCH:

cmo- 10 I I 0on1 cm-o 0-1 H- CONH ll OCH; If .c1 0H,-co-cH-co.NH-

(31 being a water insoluble yellow powder. 6- T m n a o dyestuf! of. the. followin QQHB v formula:

BO|.NH.COH| '20 00m being a water-insoluble yellow powder, I v CH O 4. The monoazo dyestufi of the following formula: N

ILL CH; SIONE 0Hr-co-en-oo.2m

non. 01

CEIQ 09H? t I being a water-insoluble yellow powder.

E 0921- ERNST FISCHER. I References Cited in the file of this patent c3760 UNITED-STATES PATENTS o c H 7 Number Name Date 40 2,142,594 Zitscher et a1. Jan. 3, 1939 G1 2,427,537 Straub et a1. Sept. 16, 1947 FOREIGN PATENTS Number Country Date being a water-insoluble yellow powder. 479,848 Great Britain Feb. 10, 1938 

3. THE MONOAZO DYESTUFF OF THE FOLLOWING FORMULA: 